Distillation of oil



June 7, 1932. s. P. MILLER 1,862,493

DISTILLATION OF OIL Filed March 29. 1927 4 sheets-sheet 1 (omai/255k 5 Afm/wf@ omas @yg/g ffm/V ATTORNEY June 7, 1932. s. P. MILLER 1,862,493

DISTILLATION oF OIL Filed March 29, 1927 4 Sheets-Sheet 2 awa INVENTOR MEM/#MM @L 2mm ATTORNEYS Qian@ 79 w32. 5. P. MHLLER 393629493 DISTILLATION oF OIL Filed March 29. 1927 4 sheets-sheet 3 INVEN OR WMM ATTORNEYS Jun@ 3,32.,

. p. MLLER DISTILLATION OF OIL Filed March 29, 1927 ams 4 Sheets-Sheet 4 INVENTOR ATTORNEYS Patented June 7, 1932 UNITED STATES yPATE STUART PARMELEE MILLER, QF TENAFLY, N EW JERSEY, ASSIGNR .T THE BARRETT COMPANY, 0F NEW YORK, N. Y., A CORPORATION QF NEW JERSEY DISTILLATIQN OF OIL Application led March 29, 1927.' Serial No, 179,2[)9 4 rlhis invention relates to improvements in the operation of coke ovens, and partlcularly to the utilization of the oils recovered from the coke-oven gases to cool the latter and particularly to facilitate the operation of the collector main through which the gases pass from the ovens.

ln the ordinary operation of by-product coke ovens the gases produced by the coking operation pass from the individual .ovens through uptake pipes and goose-necks to a collector main common to the ovens `of the battery. The gases, commonly known as foul gases, leave the ovens at high temperatures, e. g., 600 to 700 C. or higher, and carry a considerable proportion of tar and oil constituents. Ordinarily the gases are cooled as rapidly as possible by the application of sprays of ammonia liquor or ammonia liquor and tar in the goose-necks and collector main. The rapid cooling causes separation of the tar containing the heavier oils in the collector main. Further cooling is effected in the cross-overV main which connects the collectorvmain to the condensing system and an additional quantity of tar carrying both heavier and lighter oils is thus separated. The collected tar, together with that from the gas coolers, isy shipped from the coke-oven plant to a tar-distillation plant for distillation and separation of the oils and the production of pitches of varying qualities.. Owing to the high temperature ofthe gases from the coke ovens, and particularly because of the enormous amount of heat carried thereby', the successful operation of the collector main in connection with these ovens has always been a serious problem. The heat carried by the gases which leave the ovens at a temperature of approximately 700o C. or higher is from twenty to thirty-live times that required for the distillation of all of'the tar contained in the gases. A certain amount of heavy tar or` pitch may separate in the collector main and such tar or pitch is subjected to the distilling effect of the gases at high temperature with the resulting formation in the main of solid hard pitch which in some cases can be removed only by shutting down the plant and scraping or digging it out. The practice of ushing the main with ammonia liquor or ammonia liquor and tar does notalways avoid the diculty. In fact, the use of waterA or ammonia liquor aggravates the condition in some cases because the 'pitches formed in the main are insoluble in water or ammonia liquor and hence are not flushed out unless an extremely large amount of liquor is employed.

The use of a large quantity of ammonia liquor for flushing the collector main introduces a further diculty because 0f the resulting lowered temperature of the gases. rlhus, by spraying ammonia liquor into the collector main in sulicient quantity to prevent accumulations of pitch therein the temperature of the gases maybe so reduced that a considerable proportion of the valuable oil constitutents which are present in the gases are condensed and are thrown down with they tar and can be recovered therefrom only by the subsequent distillation.

It is the object of the present invention to provide an improved process and apparatus wherein loils recovered. as by-products from the distillation of coal can be utilized to reduce the temperature of the gases in the collector main to the point required with suitable regulation so as to avoid unnecessary cooling, the heat ofthe gases being utilized economically to distill the oils and to produce therefrom cleaner distillates, the gases being scrubbed at the same time by contact with the oils so that tar carried thereb is effectively removed and retained substantially in the collector main.

According to the-present invention the hot coke-oven gases are subjected in the goosenecks leading from the ovens to the collector main to intimate' contact with oils derived from the condensation of vapors from the coke-oven gases in the condensing system. It is desirable at the saine time to bring such oils into intimate contact with the gases in the collector main. The intimate contact of the oils with the gases results in the partial cooling of these gases from the temperature at which they normally escape from the coke ovens to that desired, that temperature ordi- 100 naril being Asuch that the major portion of theoil vapors in the gases and those derived from the vaporization of oils supplied to the collector main are retained in the gases while substantially all of the tarry materials are thrown down in the collector main and are washed therefrom by the residual oils which flow through the bottom of the main.

The operation as described prevents the deposition of hard pitch in the collector main because the pitch is soluble in the hot oil. Any such pitch which may tend ,to form on the walls or in the bottom of the main is thus flushed therefrom and carried away with the oil which can be Withdrawn continuously or intermittently from the main. To ensure such operation it is desirable to provide an amount of oil in excess of that which will be distilled by the heat of the coke-oven gases flowing through lthe main. The oil withdrawn and carrying with it tarry constituents can be recirculated through the main to be further distilled by contact with the hot gases so that eventually the desired oil constituents will be separated as vapor and can be withdrawn as such along with the gases and subsequently condensed. A

The intimate contact of the oil with the gases may be accomplished by spraying the oil into the collector main and the goose-necks leading thereto through spray nozzles although numerous other methods of attainin the desired intimacy of contact may be use A sufiicient number of spray nozzles may' be provided to ensure effective and intimate contact between the oil and the gases and the consequent removal of the heat from the gases and the distillation of a portion of the oil so introduced. It may be Adesirable also to introduce an additional quantity of oil at the end of the collector main so that it may flow therethrough to the outlet from which, as indicated, oil carrying tarryconstituents can be withdrawn at intervals or continuously and recirculated through the main or utilized.

otherwise.

The intimate contact between the oil and gases can be accomplished likewise by suitable mechanical agitation in the collector main. Thus, by providing one or more shafts extending through the main and having paddles or other agitating devices such as cones, discs, plates or the like thereon, the oil can be thrown into the stream of gases and thus caused to mingle therewith so as to achieve the desired purpose. The required agitation can be effected likewise by the introduction of compressed gases such, for example, as fuel or coke-oven gases or steam through a suitable distributor pipe immersed in tar; or suction Ts (McDaniel type ejectors) may be located in the main with their suction ends beneath the level of the tar therein.

While the invention depends primarily upon the use of oil, it may in some cases be oven batteries.

lthe higher specific 'and latent heats of water as compared with those of oils. It is possible, therefore, to add water or ammonia liquor in the proportion required to remove all heat from the gases in thecollector main except that needed for the distillation of the oil which is introduced to the collector main. Cooling of the gases to a regulated extent can be accomplished also by the addition thereto of cold gases such as fuel gas, cooled cokeoven gas, ete.

In carrying out the invention the usual coke-oven structure and the equi ment employed for the recovery of by-pro ucts therefrom canl be utilized. Thus, the coke ovens can be connected to the usual collector main from which the gases and vapors are withdrawn through a cross-over main and delivered to condensers .in which the oils are separated. These oils can be returned then for use as a cooling medium in the collector main in which they are again vaporized. The vapors thus formed are carried with the gases through the cross-over main tothe condensers where the oils are recovered and can be again used as a cooling medium. That portion of the oils which is not required for use in the collector main as a cooling medium can be withdrawn and utilized for the pui'.- poses to which such materials are adapted.

The distillation of the oil in the collector main removes from the gases passing therethrough most of the tarry constituents so that cleaner vapors are withdrawn from the collector main, and these vapors when condensed produce cleaner oils. The clean oils result, however, largely from the fact that the gases have been greatly enriched in clean oil vapors by the distillation of oil in the collector main. The tar fog normally present in the gases and contaminating the oils is, in the case of enriched gases, of relatively small importance due to its smallproportion of the oils as compared with those recovered under normal conditions. The invention can be utilized, therefore, to distill dirty oils or those contaminated with tar or pitch. Such oils may be those produced by the cokeoven battery in which the invention is utilized or they may be products of other coke- The heat available in the coke-oven gases from a 'single batter is many times that required to distill all o the tar and oil produced by that battery and consequently the application of the invention to a single battery will permit the distillation of all of the oils produced by a number of batteries. The resulting vapors being freed substantially from tar and pitch constituents can be condensed if desired in a fractional manner by cooling the gases and vapors sucdii' wherein the gases are cooled by the applicationl of ammonia liquor or ammonia liquor and tar in accordance with the usual practice. In such a case the usual collector main may be provided with the ordinary condensing system and the oils recovered therefrom can be employed in the short collector main in accordance with the invention. The distillate from the short collector main can be cooled in a separate condensing system consisting preferably of a number of fractional condensers so that oil fractions having de sired characteristics can be produced directly as the result of the operation of the short main;

collector main and by the utilization of a portion of the heat in the coke-oven gases. The present invention is of more or less general application to the distillation of oils and the recovery of distillates therefrom. The invention involves utilization of the hot coke-oven gases'for the distillation of oil by bringing the oil into direct contact therewith. The invention will be further illustrated by the following more detailed description which should be read with the accompanying drawings showing apparatus embodying the invention and adapted for the practice thereof, but it is intended and will be understood that the invention is not limited to specific details of the apparatus as illustrated in the drawings, in which Fig. 1 is a plan view of a portion of a cokeoven illustrating the application of the invention thereto;

Fig. 2 is an end elevation, partially in section. of the structure illustrated in Fig. 1;

Fig. 3 is an enlarged view, partially in section, showing ,the sprays in the collector Fig. 4 is a View similar to Fig.. 3 illustrating agitating means on the collector main; and

Fig. 5 is a plan view illustrating Athe application of the invention in a separate short collector main.

Referring to the drawings, 5 indicates a battery of coke ovens having individual uptake pipes and goose-necks 6 which connect the ovens with a collector main 7. The latter may be of any usual form and construction and is designed to receive all of the gases from the individual coke ovens and to deliver them through a centre box 8 to a cross-over main 9 which is connected to the condensing apparatus hereinbefore described.

The collector main is provided with a plurality of spray nozzles 10 distributed throughout its length. A pipe 12 supplies oil to the s ray nozzles 10 and to spray nozzles 13 in tlie goose-necks leading to the collector main. A pump 14 is provided to force the oil from a receptacle 15 to the spray nozzles. A pipe 17 is connected to the pipe 12 and to the end of the collector main to permit the introduction of oil in addition to that supplied through the spray nozzles. The oil carrying tarrv constituents therewith can be withdrawn through a pipe 18 and recirculated through a pump 19 and a pipe 20, or all or a portion of the oil can be withdrawn through a pipe 21.

As hereinbefore described, the opera-tion of the collector main involves the maintenance therein and the circulation therethrough of a suliicient quantity of oil to reduce the temperature of the gases in the main to the desired point and to prevent the accumulation of hard pitch in the bottom or on the exposed surfaces'thereof. The oil carrying the tar and pitch may be withdrawn continuously or intermittently as desired. The oil which is introduced through the spray nozzles is subjected by reason of its subdivision to intimate contact with the hot cokeoven gases which enter the collector main. This intimate Contact of the gases with the oil effectsa substantial distillation thereof and the vapors thus produced join the gases which leave the collector main through the cross-oven main.

The gases which escape from the centre box 8 to the cross-over main 9 carry therewith a large proportion of volatile constituents of the oil which enters the collector main and a-re 'to a considerable degree freed not only from entrained heavy tar constituents which are not volatile at the temperature of operation of the collector main but also from insoluble entrained matter. These gases may be subjected in the cross-over main to contact with ammonia liquor or ammonia liquor and oil delivered thereto through' a plurality of spray nozzles 23 supplied by a pipe 24 from any available source. From the crossover main the liquid containing any tar or oil constituents, together with the ammonia liquor, is delivered through a pipe 24 to a decanter 25 in which the ammonia liquor can be separated 'and returned, for example, through a pipe 24 to the cross-over main. The tar or Voil from the decanter can be delivered through a pipe 26 to a receptacle 26.

'The gases may be passed through condensers 27'and thence to an exhauster 28 which maintains the pressure balance in the system. The oils separated in the condensers 27 can be withdrawn through a decanter 29 wherein the oils are separated from the ammonia liquor. These oils can he delivered through a. pipe 30 to the receptacle l5 whence they are withdrawn by the pump lll and delivered to the spray nozzles in the collector main for the purpose of cooling the gases therein, or they may be removed from the system.

In Fig. 4c of the drawings the collector main is provided with agitating paddles 3l.`

on a shaft 32 which may be actuated from any suitable source of power to cause the desired agitation of the oil in the collector main. The agitating means may he employed as a substitute for or adjunct to the spray nozzles as hereinbefore described for the purpose of maintaining an intimate contact with the oil in finely divided 'form with the hot cokeoven gases passing through the collector main.

In Fig. 5 of the drawings most of the ovens of the coke-oven 'cattery are connected hy uptake pipes and goose-necks 83 to a collector main 34 having a centre loon 35 which communicates with a cross-over main. 36 leading to condensers @Zand to an exhauster 3?', the structure descri i l sing that employed usually 1n by-prc recovery systems con nected to coke .or e collector main is adapted to he su itT ammonia liquor or ammonia liquor l 'the purpose oi cooling the gases tno ein.

A short collector rn in 3d disposed prei erably at the rear or "i nected to a nurer ci over pipes and goes provided to per n a dive; sion c., from the selected. colse ovens into the short collector main when the lPN n loeing operated, 'the ga :2^ otherwise 'to the usual The short collector main provided with spray nozzles 3&3, similar spray nozzles losing disposed in the goose-necks leading thereto so that the gases vora the colse ovens can i he subjected to intimate contact with oil derived, 'for example, from the condensers 37 or from any other source. The oil is supplied in sufficient quantity and vunder regula tion to eiect the desired cooling in the collector main and to distill the oil. Suilicient oil is supplied to avoid the accumulation `of hard pitch as the result of distillation oll terry constituents of the gases.

The vapors r the distillation of the oil are withdrawn vvith the gases and carried through cross-over main 39 to a series of fractional condenscrs all) wherein the clean oils are condensed in ractionsand can be withdrawn and utilizedV for any de sircd purpose.v The remaining gases may be delivered through a pipe il the exhauster 37 and thence delivered with the remaining gases from the system to the usual equipment employed for further treatment of these gases.

The arrangement as described permits the operation of the coke-oven in theusual manner and the utilization of a portion of the heat of the coke-oven gases `for the distillation of oils for the purpose of producing cleaner distillates. It likewise avoids the diiliculties experienced heretofore in the 0peration of the collector main by preventingaccumulation of hard pitch therein. At the same time the gases are cooled ei'ectively and are scrubbed to remove tarry constituents therefrom.

The advantages of the invention have been set forth in some detail and the preferred embodiments have been described. It is to be understood, however, that various changes may be made in the form and arrangement of the apparatus and in the operation as de scribed without departing from the invention or sacrificing the advantages enumerated or any other advantageous results which may be accomplished by the application of the principles set forth.

l. The improvement in the distillation of tar in connection with the distillation of coal in coke ovens having a collector vmain connected to the individual ovens ol a battery of volatilized residue of such oil in the collectorl main, withdrawing the gases thus enriched from the collector main vvhile still hot and cooling them'to separate oils therefrom.

2. The improvement in the distillation of tar in connection with 'the distillation of coal in coke ovens having a collector main connected to the individual ovens of a battery of ovens by uptake pipes leading from said ovens and .gooseneclrs `which comprises destructively distilling coal in the ovens spraying oils derived from the condensation of vapors from the coke oven gases into the coal distillation gases as they pass through the uptake pipes and goose-necks and are still hot so as to distill the oil., collecting the nonvolatilized residue ozf such oil the collector main, supplying additional oil to the collector main, bringing the 'oil into intimate Contact with the gases passing through the main to thereby distill the oil9 withdrawing the gases thus enriched from the Vcollector main While still hot and cooling them to ernaar Pani/innen Minnen. 

